Metal-organic framework materials for gaseous hydrocarbon storage

ABSTRACT

The present invention relates to a method of storing a liquefied gas in a container containing a metal-organic framework material, the container filled with such a gas, a process for filling container and the use of the container to release the gas.

The present invention relates to a method of storing a liquefied gas ina container containing a metal-organic framework material, the containerfilled with such a gas, a process for filling container and the use ofthe container to release the gas.

Liquefied gas, especially propane or mixtures of propane and butane, isoften used as portable fuel supply. Therefore, the gas is stored in apressure resistant bottle or tank under a pressure which is high enoughto store the gas in the bottle or tank in its liquid status. Theliquefied gases are characterized by having a boiling point which is inthe range of about −50° C. to about 10° C. Therefore, normally apressure of 20 bar or higher is necessary to convert the gases to theirliquid state at room temperature.

However, there is a demand for the storage of gases which are normallyconsidered as liquefied gases under a pressure which is less than theaforementioned minimum pressure to keep the gases in their liquid state.One of the most important reasons is caused by safety provisions forpressurized vessels.

Conventional bottles or the like do not provide sufficient space toefficiently store the gases in the low pressure range.

Other ways to store gases are given by absorbing the desired gas in aporous material. Such material may be of inorganic nature like zeolitesor of organic nature like metal organic frameworks (MOF).

US 2003/0148165 A1 describes in general the storage of gases using MOFs.

There is a demanding need to provide methods to suitably store liquefiedgases in their gaseous state at a low pressure range.

Thus, the object of the invention is to provide a method for storinggases known as liquefied gases in their gaseous state in a low pressurerange in amounts which are sufficiently high.

The object is solved by a method of storing a liquefied gas in acontainer having an entrance opening and optionally a separate exitopening for allowing the liquefied gas to enter or exit the containerand a gas-tight maintaining mechanism capable of maintaining theliquefied gas in its gaseous state in a predefined amount and under apredefined pressure inside the container and containing a metal-organicframework material (MOF) comprising at least one metal ion and at leastone at least bidentate organic compound, which is coordinately bound tosaid metal ion, wherein the ratio of the pressure in the container to apressure necessary for the storage of the same amount of liquefied gasat the same temperature in the container without comprising the MOF isat most 0.2.

Surprisingly, it was found that a container comprising a MOF can uptakean unexpected high amount of liquefied gas compared to the situationwhere no MOF is used. This affords the storage of an efficiently highamount of liquefied gas in a low pressure range using an at least 5-foldlower pressure.

FIG. 1 shows the general curve progression of the uptake of a liquefiedgas (here: propane as an example) in a container with (curve A) andwithout (curve B) a MOF.

Within the meaning of the present invention the term “liquefied gas”preferably indicates a gas or mixture of different gases which can beconverted in their liquid state under a pressure of up to 40 bardepending on the temperature, however, room temperature is preferred.Moreover, according to the present invention the term “liquefied gas”does not automatically indicate a gas in its liquefied status.

Properties of gases important in industrial applications, compressedgases, gas containers used and handling instructions can be referred toin ‘Handbook of Compressed Gases’, 3^(rd) Edition, Van NostrandReinhold, N.Y., 1989 and are incorporated herein by reference.

Preferably, the liquefied gas is selected from the group consisting ofhalogenated C₁-C₁₀ hydrocarbon, propane, butane, isobutane and mixturesthereof. More preferred the liquefied gas is propane.

Due to the low pressure range used according to the present inventionthe shape and material of the container does not necessarily fulfil therequirements of pressurized vessels. Preferably, the container accordingto the present invention is of a non-cylidrical shape. The containermaterial does not necessarily consist of stainless steel.

The container comprises an entrance opening and optionally a separateexit opening for allowing the liquefied gas to enter or exit thecontainer and a gas-tight maintaining mechanism capable of maintainingthe liquefied gas. Preferably the entrance and exit opening are the sameequipped with a conventional valve used as the gas-tight maintainingmechanism.

In a preferred embodiment the pressure is more than 0.1 bar and lessthan 20 bar. More preferably, the pressure is more than 1 bar and lessthan 20 bar, even more preferred more than 1 bar and less than 10 bar.

The amount of liquefied gas in the container is at least 2 g/l. Theratio of the pressure in the container to a pressure necessary for thestorage of the same amount of liquefied gas at the same temperature inthe container without comprising the MOF is at most 0.2. Preferably, theratio is at most 0. I and more preferred at most 0.05.

Another aspect of the present invention is a container filled withliquefied gas in a predefined amount and under a predefined pressurehaving an entrance opening and optionally a separate exit opening forallowing the liquefied gas to enter or exit the container and agas-tight maintaining mechanism capable of maintaining the liquefied gasin its gaseous state in a predefined amount and under a predefinedpressure inside the container and containing a metal-organic frameworkmaterial (MOF) comprising at least one metal ion and at least one atleast bidentate organic compound, which is coordinately bound to saidmetal ion, wherein the ratio of the pressure in the container to apressure necessary for the storage of the same amount of liquefied gasat the same temperature in the container without comprising the MOF isat most 0.2.

Yet another aspect of the present invention is a process for filling acontainer having an entrance opening and optionally a separate exitopening for allowing the liquefied gas to enter or exit the containerand a gas-tight maintaining mechanism capable of maintaining theliquefied gas in its gaseous state inside the container and containing ametal-organic framework material (MOF) comprising at least one metal ionand at least one at least bidentate organic compound, which iscoordinately bound to said metal ion, with a liquefied gas up to apredefined amount and a predefined pressure so that the ratio of thepressure in the container to a pressure necessary for the storage of thesame amount of liquefied gas at the same temperature in the containerwithout comprising the MOF is at most 0.2, comprising the step

-   -   contacting the entrance opening of the container with a bottle        of the liquefied gas, wherein the gas is in its liquid state or        compressed state, such that the pressure in the feed container        exceeds the pressure in the container which is to be filled.

Yet another aspect of the present invention is the use of a containeraccording to the present invention for the controlled release ofliquefied gas.

Suitable MOFs are in known in the art. They can be used as powder butpreferably, the MOFs are used as shaped bodies, more preferred asextrudates or tablets.

The MOF containing powder has a fine powdery to powdery grain size andmay contain or consist of crystallites (small crystals). According tothe present invention the term “powder” is used for all forms describedabove as well as mixtures thereof. The maximum grain size of the powderis preferably less than 0.2 mm for each direction.

The shaped body can have any form suitable for the planned use.Preferably, it is pellet, tablet or bar shaped. In the context of thepresent invention, the term “shaped body” preferably refers to any solidbody that extends to at least 0.2 mm in at least one direction in space.No other restrictions apply, i.e., the body may take any conceivableshape and may extend in any direction by any length so long as itpreferably extends to at least 0.2 mm in one direction. In a morepreferred embodiment, the shaped bodies do not extend to more than 50 mmand not to less than 0.2 mm in all directions. In a further preferredembodiment, this range is limited from 1 mm to 16 mm, preferably from1.5 mm to 5 mm.

As far as the geometry of these shaped bodies is concerned, spherical orcylindrical bodies are also preferred, as well as disk-shaped pellets orany other suitable geometry such as honeycombs, meshes, hollow bodies,wire arrangements etc.

The MOF containing powder includes a metal-organic framework materialwhich is built up from metal ions and at least bidentate organiccompounds coordinately bound to said metal ion. The MOF as suchcomprises cavities which are accessible by pores. One cavity is definedby eight metal ions linked together by at least bidentate organiccompounds.

As has been mentioned above, the MOF is described in, for example, U.S.Pat. No. 5,648,508, EP-A-0 709 253, M. O'Keeffe et al., J. Sol. StateChem., 152 (2000) p. 3-20, H. Li et al., Nature 402 (1999) p. 276 seq.,M. Eddaoudi et al., Topics in Catalysis 9 (1999) p. 105-111, B. Chen etal., Science 291 (2001) p. 1021-23 and DE-A-101 11 230.

The MOFs, as used in the present invention, comprise pores, particularlymicro- and/or mesopores. Micropores are defined as being pores having adiameter of 2 nm or below and mesopores as being pores having a diameterin the range of 2 nm to 50 nm, according to the definition given in PureApplied Chem. 45, p. 71 seq., particularly on p. 79 (1976). The presenceof the micro- and/or mesopores can be monitored by sorption measurementswhich determine the capacity of the metal-organic framework materialsfor nitrogen uptake at 77 K according to DIN 66131 and/or DIN 66134.

For example, a type-I-form of the isothermal curve indicates thepresence of micropores [see, for example, paragraph 4 of M. Eddaoudi etal., Topics in Catalysis 9 (1999)]. In a preferred embodiment, thespecific surface area, as calculated according to the Langmuir model(DIN 66131, 66134, 66135) preferably is above 5 m²/g, more preferredabove 10 m²/g, even more preferably above 50 m²/g, even more preferredabove 500 m²/g, even more preferred above 1000 m²/g, even more preferredabove 1500 m²/g, even more preferred above 2500 m²/g and may increaseinto the region above 4500 m²/g. p Shaped bodies can have a lowerspecific surface area but preferably, is above 10 m²/g, more preferredabove 50 m²/g and most preferred above 500 m²/g.

As to the metal component within the framework material that is to beused according to the present invention, particularly to be mentionedare the metal ions of the main group elements and of the subgroupelements of the periodic system of the elements, namely of the groupsIa, IIa, IIIa, IVa to VIIIa and Ib to VIb. Among those metal components,particular reference is made to Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V,Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag,Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi, morepreferably to Zn, Cu, Ni, Pd, Pt, Ru, Rh and Co and most preferred Znand Cu. As to the metal ions of these elements, particular reference ismade to: Mg , Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Y³⁺, Ti⁴⁺, Zr⁴⁺, Hf⁴⁺, V⁴⁺, V³⁺,V²⁺, Nb³⁺, Ta³⁺, Cr³⁺, Mo³⁺, W³⁺, Mn³⁺, Mn²⁺, Re³⁺, Re²⁺, Fe³⁺, Fe²⁺,Ru³⁺, Ru²⁺, Os³⁺, Os²⁺, Co³⁺, Co²⁺, Rh²⁺, Rh³⁰ , Ir²⁺, Ir⁺, Ni²⁺, Ni⁺,Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁺, Ag⁺, Au⁺, Zn²⁺, Cd²⁺, Hg²⁺, Al³⁺, Ga³⁺,In³⁺, Tl³⁺, Si⁴⁺, Si²⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁺, As³⁺,As⁺, Sb⁵⁺, Sb³⁺, Sb⁺, Bi⁵⁺, Bi³⁺ and Bi⁺.

With regard to the preferred metal ions and further details regardingthe same, particular reference is made to: U.S. Pat. No. 5,648,508,particularly to col. 11, line 11 to 51, section “The Metal Ions”, whichsection is incorporated herein by reference.

In addition to the metal salts disclosed in EP-A 0 790 253 and U.S. Pat.No. 5,648,508, other metallic compounds can be used, such as sulfates,phosphates and other complex counter-ion metal salts of the main- andsubgroup metals of the periodic system of the elements. Metal oxides,mixed oxides and mixtures of metal oxides and/or mixed oxides with orwithout a defined stoichiometry are preferred. All of the abovementioned metal compounds can be soluble or insoluble.

As to the at least bidentate organic compound, which is capable ofcoordination with the metal ion, in principle all compounds can be usedwhich are suitable for this purpose and which fulfill the aboverequirements of being at least bidentate. Said organic compound musthave at least two centers, which are capable to coordinate the metalions of a metal salt, particularly with the metals of the aforementionedgroups. With regard to the at least bidentate organic compound, specificmention is to be made of compounds having

-   -   i) an alkyl group substructure, having from 1 to 10 carbon        atoms,    -   ii) an aryl group substructure, having from 1 to 5 phenyl rings,    -   iii) an alkyl or aryl amine substructure, consisting of alkyl        groups having from 1 to 10 carbon atoms or aryl groups having        from 1 to 5 phenyl rings,        said substructures having bound thereto at least one at least        bidentate functional group “X”, which is covalently bound to the        substructure of said compound, and wherein X is selected from        the group consisting of CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃,        Sn(OH)₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₃, PO₃H, AsO₃H, AsO₄H, P(SH)₃,        As(SH)₃, CH(RSH)₂, C(RSH)₃, CH(RNH₂)₂, C(RNH₂)₃, CH(ROH)₂,        C(ROH)₃, CH(RCN)₂, C(RCN)₃, wherein R is an alkyl group having        from 1 to 5 carbon atoms, or an aryl group consisting of 1 to 2        phenyl rings, and CH(SH)₂, C(SH)₃, CH(NH₂)₂, C(NH₂)₂, CH(OH)₂,        C(OH)₃, CH(CN)₂ and C(CN)₃.

Particularly to be mentioned are substituted or unsubstituted, mono- orpolynuclear aromatic di-, tri- and tetracarboxylic acids and substitutedor unsubstituted, at least one hetero atom comprising aromatic di-, tri-and tetracarboxylic acids, which have one or more nuclei.

Preferred ligands are ADC (acetylene dicarboxylate), NDC (naphtalenedicarboxylate), BDC (benzene dicarboxylate), ATC (adamantanetetracarboxylate), BTC (benzene tricarboxylate), BTB (benzenetribenzoate), MTB (methane tetrabenzoate) and ATB (adamantanetribenzoate). More preferred bidentate ligands are 1,2,3,- and1,3,5-benzene tricarboxylic acid (BCT), iosphtalic acid, terephtalicacid, 2,5-dihydroxy-terephtalic acid and2,2′-bipyridine-5,5′-dicarboxylic acid.

Besides the at least bidentate organic compound, the framework materialas used in accordance with the present invention may also comprise oneor more mono-dentate ligand(s), which is/are preferably selected fromthe following mono-dentate substances and/or derivatives thereof:

-   -   a. alkyl amines and their corresponding alkyl ammonium salts,        containing linear, branched, or cyclic aliphatic groups, having        from 1 to 20 carbon atoms (and their corresponding ammonium        salts);    -   b. aryl amines and their corresponding aryl ammonium salts        having from 1 to 5 phenyl rings;    -   c. alkyl phosphonium salts, containing linear, branched, or        cyclic aliphatic groups, having from 1 to 20 carbon atoms;    -   d. aryl phosphonium salts, having from 1 to 5 phenyl rings;    -   e. alkyl organic acids and the corresponding alkyl organic        anions (and salts) containing linear, branched, or cyclic        aliphatic groups, having from 1 to 20 carbon atoms;    -   f. aryl organic acids and their corresponding aryl organic        anions and salts, having from 1 to 5 phenyl rings;    -   g. aliphatic alcohols, containing linear, branched, or cyclic        aliphatic groups, having from 1 to 20 carbon atoms;    -   h. aryl alcohols having from 1 to 5 phenyl rings;    -   i. inorganic anions from the group consisting of:

sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogenphosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite,chloride, chlorate, bromide, bromate, iodide, iodate, carbonate,bicarbonate, and the corresponding acids and salts of the aforementionedinorganic anions,

-   -   j. ammonia, carbon dioxide, methane, oxygen, ethylene, hexane,        benzene, toluene, xylene, chlorobenzene, nitrobenzene,        naphthalene, thiophene, pyridine, acetone, 1-2-dichloroethane,        methylenechloride, tetrahydrofuran, ethanolamine, triethylamine        and trifluoromethylsulfonic acid.

Further details regarding the at least bidentate organic compounds andthe mono-dentate substances, from which the ligands of the frameworkmaterial as used in the present application are derived, can be takenfrom EP-A 0 790 253, whose respective content is incorporated into thepresent application by reference.

Within the present application, framework materials of the kinddescribed herein, which comprise Zn²⁺ as a metal ion and ligands derivedfrom terephthalic acid as the bidentate compound, are particularlypreferred. Said framework materials are known as MOF-5 in theliterature.

Further metal ions, at least bidentate organic compounds andmono-dentate substances, which are respectively useful for thepreparation of the framework materials used in the present invention aswell as processes for their preparation are particularly disclosed inEP-A 0 790 253, U.S. Pat. No. 5,648,508 and DE-A-101 11 230.

As solvents, which are particularly useful for the preparation of MOF-5,in addition to the solvents disclosed in the above-referencedliterature, dimethyl formamide, diethyl formamide andN-methylpyrollidone, alone, in combination with each other or incombination with other solvents may be used. Within the preparation ofthe framework materials, particularly within the preparation of MOF-5,the solvents and mother liquors are recycled after crystallization inorder to save costs and materials.

The pore sizes of the metal-organic framework can be adjusted byselecting suitable organic ligands and/or bidendate compounds(=linkers). Generally, the larger the linker the larger the pore size.Any pore size that is still supported by a MOF in the absence of a hostand at temperatures of at least 200° C. is conceivable. Pore sizesranging from 0.2 nm to 30 nm are preferred, with pore sizes ranging from0.3 nm to 3 nm being particularly preferred.

With regard to the shaped bodies other pore sizes may occur. Preferably,more than 50% of the total pore volume, more preferred more than 75% ofthe total pore volume, is formed by pores having a pore diameter of upto 1000 nm.

Preferably, the bigger part of the pore volume is formed by pores comingfrom two distinct diameter ranges. Therefore, it is more preferred thatmore than 25%, even more preferred more than 50%, of the total porevolume is formed by pores having a diameter in the range of from 100 nmto 800 nm and that preferably more than 15%, even more preferred morethan 25%, of the total pore volume is formed by pores having a diameterof up to 10 nm. The pore distribution can be determined byHg-porosimetry (DIN 66133).

In the following, examples of metal-organic framework materials (MOFs)are given to illustrate the general concept given above. These specificexamples, however, are not meant to limit the generality and scope ofthe present application.

By way of example, a list of metal-organic framework materials alreadysynthesized and characterized is given below. This also includes novelisoreticular metal organic framework materials (IR-MOFs), which may beused in the framework of the present application. Such materials havingthe same framework topology while displaying different pore sizes andcrystal densities are described, for example in M. Eddouadi et al.,Science 295 (2002) 469, which is incorporated into the presentapplication by reference.

The solvents used are of particular importance for the synthesis ofthese materials and are therefore mentioned in the table. The values forthe cell parameters (angles α, β and γ as well as the spacings a, b andc, given in Angstrom) have been obtained by x-ray diffraction andrepresent the space group given in the table as well. Ingredients molarratios Space MOF-n M + L Solvents α β γ a b c Group MOF-0 Zn(NO₃)₂.6H₂Oethanol 90 90 120 16.711 16.711 14.189 P6(3)/ H₃(BTC) Mcm MOF-2Zn(NO₃)₂.6H₂O DMF 90 102.8 90 6.718 15.49 12.43 P2(1)/n (0.246 mmol)toluene H₂(BDC) 0.241 mmol) MOF-3 Zn(NO₃)₂.6H₂O DMF 99.72 111.11 108.49.726 9.911 10.45 P-1 (1.89 mmol) MeOH H₂(BDC) (1.93 mmol) MOF-4Zn(NO₃)₂.6H₂O ethanol 90 90 90 14.728 14.728 14.728 P2(1)3 (1.00 mmol)H₃(BTC) (0.5 mmol) MOF-5 Zn(NO₃)₂.6H₂O DMF 90 90 90 25.669 25.669 25.669Fm-3m (2.22 mmol) chlorobenzene H₂(BDC) (2.17 mmol) MOF-38 Zn(NO₃)₂.6H₂ODMF 90 90 90 20.657 20.657 17.84 I4cm (0.27 mmol) chlorobenzene H₃(BTC)(0.15 mmol) MOF-31 Zn(NO₃)₂.6H₂O ethanol 90 90 90 10.821 10.821 10.821Pn(−3)m Zn(ADC)₂ 0.4 mmol H₂(ADC) 0.8 mmol MOF-12 Zn(NO₃)₂.6H₂O ethanol90 90 90 15.745 16.907 18.167 Pbca Zn₂(ATC) 0.3 mmol H₄(ATC) 0.15 mmolMOF-20 Zn(NO₃)₂.6H₂O DMF 90 92.13 90 8.13 16.444 12.807 P2(1)/c ZnNDC0.37 mmol chlorobenzene H₂NDC 0.36 mmol MOF-37 Zn(NO₃)₂.6H₂O DEF 72.3883.16 84.33 9.952 11.576 15.556 P-1 0.2 mmol chlorobenzene H₂NDC 0.2mmol MOF-8 Tb(NO₃)₃.5H₂O DMSO 90 115.7 90 19.83 9.822 19.183 C2/c Tb₂(ADC) 0.10 mmol MeOH H₂ADC 0.20 mmol MOF-9 Tb(NO₃)₃.5H₂O DMSO 90 102.0990 27.056 16.795 28.139 C2/c Tb₂ (ADC) 0.08 mmol H₂ADB 0.12 mmol MOF-6Tb(NO₃)₃.5H₂O DMF 90 91.28 90 17.599 19.996 10.545 P21/c 0.30 mmol MeOHH₂ (BDC) 0.30 mmol MOF-7 Tb(NO₃)₃.5H₂O H₂O 102.3 91.12 101.5 6.14210.069 10.096 P-1 0.15 mmol H₂(BDC) 0.15 mmol MOF-69A Zn(NO₃)₂.6H₂O DEF90 111.6 90 23.12 20.92 12 C2/c 0.083 mmol H₂O₂ 4,4′BPDC MeNH₂ 0.041mmol MOF-69B Zn(NO₃)₂.6H₂O DEF 90 95.3 90 20.17 18.55 12.16 C2/c 0.083mmol H₂O₂ 2,6-NCD MeNH₂ 0.041 mmol MOF-11 Cu(NO₃)₂.2.5H₂O H₂O 90 93.8690 12.987 11.22 11.336 C2/c Cu₂(ATC) 0.47 mmol H₂ATC 0.22 mmol MOF-11 9090 90 8.4671 8.4671 14.44 P42/ Cu₂(ATC) mmc dehydr. MOF-14Cu(NO₃)₂.2.5H₂O H₂O 90 90 90 26.946 26.946 26.946 Im-3 Cu₃ (BTB) 0.28mmol DMF H₃BTB EtOH 0.052 mmol MOF-32 Cd(NO₃)₂.4H₂O H₂O 90 90 90 13.46813.468 13.468 P(−4) Cd(ATC) 0.24 mmol NaOH 3m H₄ATC 0.10 mmol MOF-33ZnCl₂ H₂O 90 90 90 19.561 15.255 23.404 Imma Zn₂ (ATB) 0.15 mmol DMFH₄ATB EtOH 0.02 mmol MOF-34 Ni(NO₃)₂.6H₂O H₂O 90 90 90 10.066 11.16319.201 P2₁2₁2₁ Ni(ATC) 0.24 mmol NaOH H₄ATC 0.10 mmol MOF-36Zn(NO₃)₂.4H₂O H₂O 90 90 90 15.745 16.907 18.167 Pbca Zn₂ (MTB) 0.20 mmolDMF H₄MTB 0.04 mmol MOF-39 Zn(NO₃)₂ 4H₂O H₂O 90 90 90 17.158 21.59125.308 Pnma Zn₃O(HBTB) 0.27 mmol DMF H₃BTB EtOH 0.07 mmol NO305FeCl₂.4H₂O DMF 90 90 120 8.2692 8.2692 63.566 R-3c 5.03 mmol formic acid86.90 mmol NO306A FeCl₂.4H₂O DEF 90 90 90 9.9364 18.374 18.374 Pbcn 5.03mmol formic acid 86.90 mmol NO29 Mn(Ac)₂.4H₂O DMF 120 90 90 14.16 33.52133.521 P-1 MOF-0 0.46 mmol like H₃BTC 0.69 mmol BPR48A2 Zn(NO₃)₂ 6H₂ODMSO 90 90 90 14.5 17.04 18.02 Pbca 0.012 mmol toluene H₂BDC 0.012 mmolBPR69B1 Cd(NO₃)₂ 4H₂O DMSO 90 98.76 90 14.16 15.72 17.66 Cc 0.0212 mmolH₂BDC 0.0428 mmol BPR92A2 Co(NO₃)₂.6H₂O NMP 106.3 107.63 107.2 7.530810.942 11.025 P1 0.018 mmol H₂BDC 0.018 mmol BPR95C5 Cd(NO₃)₂ 4H₂O NMP90 112.8 90 14.460 11.085 15.829 P2(1)/n 0.012 mmol H₂BDC 0.36 mmolCuC₆H₄O₆ Cu(NO₃)₂.2.5H₂O DMF 90 105.29 90 15.259 14.816 14.13 P2(1)/c0.370 mmol chlorobenzene H₂BDC(OH)₂ 0.37 mmol M(BTC) Co(SO₄) H₂O DMFSame as MOF-0 MOF- 0.055 mmol 0like H₃BTC 0.037 mmol Tb(C₆H₄O₆)Tb(NO₃)₃.5H₂O DMF 104.6 107.9 97.147 10.491 10.981 12.541 P-1 0.370 mmolchlorobenzene H₂(C₆H₄O₆) 0.56 mmol Zn ZnCl₂ DMF 90 120 90 9.4168 9.41688.464 P(−3)1m (C₂O₄) 0.370 mmol chlorobenzene oxalic acid 0.37 mmolCo(CHO) Co(NO₃)₂.5H₂O DMF 90 91.32 90 11.328 10.049 14.854 P2(1)/n 0.043mmol formic acid 1.60 mmol Cd(CHO) Cd(NO₃)₂.4H₂O DMF 90 120 90 8.51688.5168 22.674 R-3c 0.185 mmol formic acid 0.185 mmol Cu(C₃H₂O₄)Cu(NO₃)₂.2.5H₂O DMF 90 90 90 8.366 8.366 11.919 P43 0.043 mmol malonicacid 0.192 mmol Zn₆ Zn(NO₃)₂.6H₂O DMF 90 95.902 90 19.504 16.482 14.64C2/m (NDC)₅ 0.097 mmol chlorobenzene MOF-48 14 NDC H₂O₂ 0.069 mmolMOF-47 Zn(NO₃)₂ 6H₂O DMF 90 92.55 90 11.303 16.029 17.535 P2(1)/c 0.185mmol chlorobenzene H₂(BDC[CH₃]₄) 0.185 mmol H₂O₂ MO25 Cu(NO₃)₂.2.5H₂ODMF 90 112.0 90 23.880 16.834 18.389 P2(1)/c 0.084 mmol BPhDC 0.085 mmolCu-Thio Cu(NO₃)₂.2.5H₂O DEF 90 113.6 90 15.4747 14.514 14.032 P2(1)/c0.084 mmol thiophene dicarboxylic 0.085 mmol ClBDC1 Cu(NO₃)₂.2.5H₂O DMF90 105.6 90 14.911 15.622 18.413 C2/c 0.084 mmol H₂(BDCCl₂) 0.085 mmolMOF- Cu(NO₃)₂.2.5H₂O DMF 90 90 90 21.607 20.607 20.073 Fm3m 101 0.084mmol BrBDC 0.085 mmol Zn₃(BTC)₂ ZnCl₂ DMF 90 90 90 26.572 26.572 26.572Fm-3m 0.033 mmol EtOH H₃BTC base 0.033 mmol added MOF-j Co(CH₃CO₂)₂.4H₂OH₂O 90 112.0 90 17.482 12.963 6.559 C2 (1.65 mmol) H₃(BZC) (0.95 mmol)MOF-n Zn(NO₃)₂.6H₂O ethanol 90 90 120 16.711 16.711 14.189 P6(3)/mcm H₃(BTC) PbBDC Pb(NO₃)₂ DMF 90 102.7 90 8.3639 17.991 9.9617 P2(1)/n (0.181mmol) ethanol H₂(BDC) (0.181 mmol) Znhex Zn(NO₃)₂.6H₂O DMF 90 90 12037.1165 37.117 30.019 P3(1)c (0.171 mmol) p- H₃BTB xylene (0.114 mmol)ethanol AS16 FeBr₂ DMF 90 90.13 90 7.2595 8.7894 19.484 P2(1)c 0.927mmol anhydr. H₂(BDC) 0.927 mmol AS27-2 FeBr₂ DMF 90 90 90 26.735 26.73526.735 Fm3m 0.927 mmol anhydr. H₃(BDC) 0.464 mmol AS32 FeCl₃ DMF 90 90120 12.535 12.535 18.479 P6(2)c 1.23 mmol anhydr. H₂(BDC) ethanol 1.23mmol AS54-3 FeBr₂ DMF 90 109.98 90 12.019 15.286 14.399 C2 0.927 anhydr.BPDC n- 0.927 mmol propanol AS61-4 FeBr₂ pyridine 90 90 120 13.01713.017 14.896 P6(2)c 0.927 mmol anhydr. m-BDC 0.927 mmol AS68-7 FeBr₂DMF 90 90 90 18.3407 10.036 18.039 Pca2₁ 0.927 mmol anhydr. m-BDCPyridine 1.204 mmol Zn(ADC) Zn(NO₃)₂.6H₂O DMF 90 99.85 90 16.764 9.3499.635 C2/c 0.37 mmol chlorobenzene H₂(ADC) 0.36 mmol MOF-12Zn(NO₃)₂.6H₂O ethanol 90 90 90 15.745 16.907 18.167 Pbca Zn₂ (ATC) 0.30mmol H₄(ATC) 0.15 mmol MOF-20 Zn(NO₃)₂.6H₂O DMF 90 92.13 90 8.13 16.44412.807 P2(1)/c ZnNDC 0.37 mmol chlorobenzene H₂NDC 0.36 mmol MOF-37Zn(NO₃)₂.6H₂O DEF 72.38 83.16 84.33 9.952 11.576 15.556 P-1 0.20 mmolchlorobenzene H₂NDC 0.20 mmol Zn(NDC) Zn(NO₃)₂.6H₂O DMSO 68.08 75.3388.31 8.631 10.207 13.114 P-1 (DMSO) H₂NDC Zn(NDC) Zn(NO₃)₂.6H₂O 90 99.290 19.289 17.628 15.052 C2/c H₂NDC Zn(HPDC) Zn(NO₃)₂.4H₂O DMF 107.9105.06 94.4 8.326 12.085 13.767 P-1 0.23 mmol H₂O H₂(HPDC) 0.05 mmolCo(HPDC) Co(NO₃)₂.6H₂O DMF 90 97.69 90 29.677 9.63 7.981 C2/c 0.21 mmolH₂O/ H₂ (HPDC) ethanol 0.06 mmol Zn₃(PDC)2.5 Zn(NO₃)₂.4H₂O DMF/ 79.3480.8 85.83 8.564 14.046 26.428 P-1 0.17 mmol CIBz H₂(HPDC) H₂0/ 0.05mmol TEA Cd₂ Cd(NO₃)₂.4H₂O methanol/ 70.59 72.75 87.14 10.102 14.41214.964 P-1 (TPDC)2 0.06 mmol CHP H₂(HPDC) H₂O 0.06 mmol Tb(PDC)1.5Tb(NO₃)₃.5H₂O DMF 109.8 103.61 100.14 9.829 12.11 14.628 P-1 0.21 mmolH₂O/ H₂(PDC) ethanol 0.034 mmol ZnDBP Zn(NO₃)₂.6H₂O MeOH 90 93.67 909.254 10.762 27.93 P2/n 0.05 mmol dibenzylphosphate 0.10 mmol Zn₃(BPDC)ZnBr₂ DMF 90 102.76 90 11.49 14.79 19.18 P21/n 0.021 mmol 4,4′BPDC 0.005mmol CdBDC Cd(NO₃)₂.4H₂O DMF 90 95.85 90 11.2 11.11 16.71 P21/n 0.100mmol Na₂SiO₃ H₂(BDC) (aq) 0.401 mmol Cd- Cd(NO₃)₂.4H₂O DMF 90 101.1 9013.69 18.25 14.91 C2/c mBDC 0.009 mmol MeNH₂ H₂(mBDC) 0.018 mmolZn₄OBNDC Zn(NO₃)₂.6H₂O DEF 90 90 90 22.35 26.05 59.56 Fmmm 0.041 mmolMeNH₂ BNDC H₂O₂ Eu(TCA) Eu(NO₃)₃.6H₂O DMF 90 90 90 23.325 23.325 23.325Pm-3n 0.14 mmol chloro TCA benzene 0.026 mmol Tb(TCA) Tb(NO₃)₃.6H₂O DMF90 90 90 23.272 23.272 23.372 Pm-3n 0.069 mmol chloro TCA benzene 0.026mmol Formate Ce(NO₃)₃.6H₂O H₂O 90 90 120 10.668 10.667 4.107 R-3m 0.138mmol ethanol Formaic acid 0.43 mmol FeCl₂.4H₂O DMF 90 90 120 8.26928.2692 63.566 R-3c 5.03 mmol Formic acid 86.90 mmol FeCl₂.4H₂O DEF 90 9090 9.9364 18.374 18.374 Pbcn 5.03 mmol Formic acid 86.90 mmol FeCl₂.4H₂ODEF 90 90 90 8.335 8.335 13.34 P-31c 5.03 mmol Formic acid 86.90 mmolNO330 FeCl₂.4H₂O formamide 90 90 90 8.7749 11.655 8.3297 Pnna 0.50 mmolFormic acid 8.69 mmol NO332 FeCl₂.4H₂O DIP 90 90 90 10.0313 18.80818.355 Pbcn 0.50 mmol Formic acid 8.69 mmol NO333 FeCl₂.4H₂O DBF 90 9090 45.2754 23.861 12.441 Cmcm 0.50 mmol Formic acid 8.69 mmol NO335FeCl₂.4H₂O CHF 90 91.372 90 11.5964 10.187 14.945 P21/n 0.50 mmol Formicacid 8.69 mmol NO336 FeCl₂.4H₂O MFA 90 90 90 11.7945 48.843 8.4136 Pbcm0.50 mmol Formic acid 8.69 mmol NO13 Mn(Ac)₂.4H₂O ethanol 90 90 90 18.6611.762 9.418 Pbcn 0.46 mmol Bezoic acid 0.92 mmol Bipyridine 0.46 mmolNO29 Mn(Ac)₂.4H₂O DMF 120 90 90 14.16 33.521 33.521 P-1 MOF-0 0.46 mmolLike H₃BTC 0.69 mmol Mn(hfac)₂ Mn(Ac)₂.4H₂O ether 90 95.32 90 9.57217.162 14.041 C2/c (O₂CC₆H₅) 0.46 mmol Hfac 0.92 mmol Bipyridine 0.46mmol BPR43G2 Zn(NO₃)₂.6H₂O DMF 90 91.37 90 17.96 6.38 7.19 C2/c 0.0288mmol CH₃CN H₂BDC 0.0072 mmol BPR48A2 Zn(NO₃)₂ 6H₂O DMSO 90 90 90 14.517.04 18.02 Pbca 0.012 mmol toluene H₂BDC 0.012 mmol BPR49B1 Zn(NO₃)₂6H₂O DMSO 90 91.172 90 33.181 9.824 17.884 C2/c 0.024 mmol methanolH₂BDC 0.048 mmol BPR56E1 Zn(NO₃)₂ 6H₂O DMSO 90 90.096 90 14.5873 14.15317.183 P2(1)/n 0.012 mmol n- H₂BDC propanol 0.024 mmol BPR68D10 Zn(NO₃)₂6H₂O DMSO 90 95.316 90 10.0627 10.17 16.413 P2(1)/c 0.0016 mmol benzeneH₃BTC 0.0064 mmol BPR69B1 Cd(NO₃)₂ 4H₂O DMSO 90 98.76 90 14.16 15.7217.66 Cc 0.0212 mmol H₂BDC 0.0428 mmol BPR73E4 Cd(NO₃)₂ DMSO 90 92.32490 8.7231 7.0568 18.438 P2(1)/n 4H₂O toluene 0.006 mmol H₂BDC 0.003 mmolBPR76D5 Zn(NO₃)₂ DMSO 90 104.17 90 14.4191 6.2599 7.0611 Pc 6H₂O 0.0009mmol H₂BzPDC 0.0036 mmol BPR80B5 Cd(NO₃)₂.4H₂O DMF 90 115.11 90 28.0499.184 17.837 C2/c 0.018 mmol H₂BDC 0.036 mmol BPR80H5 Cd(NO₃)₂ DMF 90119.06 90 11.4746 6.2151 17.268 P2/c 4H₂O 0.027 mmol H₂BDC 0.027 mmolBPR82C6 Cd(NO₃)₂ DMF 90 90 90 9.7721 21.142 27.77 Fdd2 4H₂O 0.0068 mmolH₂BDC 0.202 mmol BPR86C3 Co(NO₃)₂ DMF 90 90 90 18.3449 10.031 17.983Pca2(1) 6H₂O 0.0025 mmol H₂BDC 0.075 mmol BPR86H6 Cd(NO₃)₂.6H₂O DMF80.98 89.69 83.412 9.8752 10.263 15.362 P-1 0.010 mmol H₂BDC 0.010 mmolCo(NO₃)₂ NMP 106.3 107.63 107.2 7.5308 10.942 11.025 P1 6H₂O BPR95A2Zn(NO₃)₂ NMP 90 102.9 90 7.4502 13.767 12.713 P2(1)/c 6H₂O 0.012 mmolH₂BDC 0.012 mmol CuC₆F₄O₄ Cu(NO₃)₂.2.5H₂O DMF 90 98.834 90 10.9675 24.4322.553 P2(1)/n 0.370 mmol chloro- H₂BDC(OH)₂ benzene 0.37 mmol Fe FormicFeCl₂.4H₂O DMF 90 91.543 90 11.495 9.963 14.48 P2(1)/n 0.370 mmol Formicacid 0.37 mmol Mg Formic Mg(NO₃)₂.6H₂O DMF 90 91.359 90 11.383 9.93214.656 P2(1)/n 0.370 mmol Formic acid 0.37 mmol MgC₆H₄O₆ Mg(NO₃)₂.6H₂ODMF 90 96.624 90 17.245 9.943 9.273 C2/c 0.370 mmol H₂BDC(OH)₂ 0.37 mmolZn ZnCl₂ DMF 90 94.714 90 7.3386 16.834 12.52 P2(1)/n C₂H₄BDC 0.44 mmolMOF-38 CBBDC 0.261 mmol MOF-49 ZnCl₂ DMF 90 93.459 90 13.509 11.98427.039 P2/c 0.44 mmol CH3CN m-BDC 0.261 mmol MOF-26 Cu(NO₃)₂.5H₂O DMF 9095.607 90 20.8797 16.017 26.176 P2(1)/n 0.084 mmol DCPE 0.085 mmolMOF-112 Cu(NO₃)₂.2.5H₂O DMF 90 107.49 90 29.3241 21.297 18.069 C2/c0.084 mmol ethanol o-Br-m-BDC 0.085 mmol MOF-109 Cu(NO₃)₂.2.5H₂O DMF 90111.98 90 23.8801 16.834 18.389 P2(1)/c 0.084 mmol KDB 0.085 mmolMOF-111 Cu(NO₃)₂.2.5H₂O DMF 90 102.16 90 10.6767 18.781 21.052 C2/c0.084 mmol ethanol o-BrBDC 0.085 mmol MOF-110 Cu(NO₃)₂.2.5H₂O DMF 90 90120 20.0652 20.065 20.747 R-3/m 0.084 mmol thiophene dicarboxylic 0.085mmol MOF-107 Cu(NO₃)₂.2.5H₂O DEF 104.8 97.075 95.206 11.032 18.06718.452 P-1 0.084 mmol thiophene dicarboxylic 0.085 mmol MOF-108Cu(NO₃)₂.2.5H₂O DBF/ 90 113.63 90 15.4747 14.514 14.032 C2/c 0.084 mmolmethanol thiophene dicarboxylic 0.085 mmol MOF-102 Cu(NO₃)₂.2.5H₂O DMF91.63 106.24 112.01 9.3845 10.794 10.831 P-1 0.084 mmol H₂(BDCCl₂) 0.085mmol Clbdc1 Cu(NO₃)₂.2.5H₂O DEF 90 105.56 90 14.911 15.622 18.413 P-10.084 mmol H₂(BDCCl₂) 0.085 mmol Cu(NMOP) Cu(NO₃)₂.2.5H₂O DMF 90 102.3790 14.9238 18.727 15.529 P2(1)/m 0.084 mmol NBDC 0.085 mmol Tb(BTC)Tb(NO₃)₃.5H₂O DMF 90 106.02 90 18.6986 11.368 19.721 0.033 mmol H₃BTC0.033 mmol Zn₃(BTC)₂ ZnCl₂ DMF 90 90 90 26.572 26.572 26.572 Fm-3m Honk0.033 mmol ethanol H₃BTC 0.033 mmol Zn₄O(NDC) Zn(NO₃)₂.4H₂O DMF 90 90 9041.5594 18.818 17.574 aba2 0.066 mmol ethanol 14NDC 0.066 mmol CdTDCCd(NO₃)₂.4H₂O DMF 90 90 90 12.173 10.485 7.33 Pmma 0.014 mmol H₂Othiophene 0.040 mmol DABCO 0.020 mmol IRMOF-2 Zn(NO₃)₂.4H₂O DEF 90 90 9025.772 25.772 25.772 Fm-3m 0.160 mmol o-Br-BDC 0.60 mmol IRMOF-3Zn(NO₃)₂.4H₂O DEF 90 90 90 25.747 25.747 25.747 Fm-3m 0.20 mmol ethanolH₂N-BDC 0.60 mmol IRMOF-4 Zn(NO₃)₂.4H₂O DEF 90 90 90 25.849 25.84925.849 Fm-3m 0.11 mmol [C₃H₇O]₂-BDC 0.48 mmol IRMOF-5 Zn(NO₃)₂.4H₂O DEF90 90 90 12.882 12.882 12.882 Pm-3m 0.13 mmol [C₅H₁₁O]₂- BDC 0.50 mmolIRMOF-6 Zn(NO₃)₂.4H₂O DEF 90 90 90 25.842 25.842 25.842 Fm-3m 0.20 mmol[C₂H₄]-BDC 0.60 mmol IRMOF-7 Zn(NO₃)₂.4H₂O DEF 90 90 90 12.914 12.91412.914 Pm-3m 0.07 mmol 1,4NDC 0.20 mmol IRMOF-8 Zn(NO₃)₂.4H₂O DEF 90 9090 30.092 30.092 30.092 Fm-3m 0.55 mmol 2,6NDC 0.42 mmol IRMOF-9Zn(NO₃)₂.4H₂O DEF 90 90 90 17.147 23.322 25.255 Pnnm 0.05 mmol BPDC 0.42mmol IRMOF-10 Zn(NO₃)₂.4H₂O DEF 90 90 90 34.281 34.281 34.281 Fm-3m 0.02mmol BPDC 0.012 mmol IRMOF-11 Zn(NO₃)₂.4H₂O DEF 90 90 90 24.822 24.82256.734 R-3m 0.05 mmol HPDC 0.20 mmol IRMOF-12 Zn(NO₃)₂.4H₂O DEF 90 90 9034.281 34.281 34.281 Fm-3m 0.017 mmol HPDC 0.12 mmol IRMOF-Zn(NO₃)₂.4H₂O DEF 90 90 90 24.822 24.822 56.734 R-3m 13 0.048 mmol PDC0.31 mmol IRMOF- Zn(NO₃)₂.4H₂O DEF 90 90 90 34.381 34.381 34.381 Fm-3m14 0.17 mmol PDC 0.12 mmol IRMOF- Zn(NO₃)₂.4H₂O DEF 90 90 90 21.45921.459 21.459 Im-3m 15 0.063 mmol TPDC 0.025 mmol IRMOF- Zn(NO₃)₂.4H₂ODEF 90 90 90 21.49 21.49 21.49 Pm-3m 16 0.0126 mmol NMP TPDC 0.05 mmol

ADC Acetylene dicarboxylic acid

NDC Naphtalene dicarboxylic acid

BDC Benzene dicarboxylic acid

ATC Adamantane tetracarboxylic acid

BTC Benzene tricarboxylic acid

BTB Benzene tribenzoate

MTB Methane tetrabenzoate

ATB Adamantane tetrabenzoate

ADB Adamantane dibenzoate

Other MOFs known in the art are MOF-177 and MOF-178.

Examples for the synthesis of these materials in form of a powder can,for example, be found in: U.S. Pat. No. 5,648,508, J. Am. Chem. Soc. 123(2001) pages 8241 seq. or in Acc. Chem. Res. 31 (1998) pages 474 seq.,which are fully encompassed within the content of the presentapplication with respect to their respective content.

The separation of the framework materials, particularly of MOF-5, fromthe mother liquor of the crystallization may be achieved by proceduresknown in the art such as solid-liquid separations, centrifugation,extraction, filtration, membrane filtration, cross-flow filtration,flocculation using flocculation adjuvants (non-ionic, cationic andanionic adjuvants) or by the addition of pH shifting additives such assalts, acids or bases, by flotation, as well as by evaporation of themother liquor at elevated temperature and/or in vacuo and concentratingof the solid.

Besides conventional methods for the preparation of MOFs a newelectrochemical way is disclosed in German patent application N^(o) 10355 087.9 as well as in international application N^(o)PCT/EP2004/013236. The new MOFs show excellent properties in relation tothe storage of liquefied gases. Therefore, the use of these MOFsaccording to the present invention is preferred.

The term “electrochemical preparation” as employed within the scope ofthe present invention relates to a preparation method in which theformation of at least one reaction product is attendant on the migrationof electrical charges or the occurrence of electrical potentials.

The term “at least one metal ion” as used within the scope of thepresent invention and subject to the electrochemical formation of MOFsrelates to embodiments according to which at least one ion of a metal orat least one ion of a first metal and at least one ion of at least onesecond metal differing from the first metal are provided by anodicoxidation.

Accordingly, the present invention comprises embodiments in which atleast one ion of at least one metal is provided via anodic oxidation andat least one ion of at least one metal is provided via a metal salt,where the at least one metal in the metal salt and the at least onemetal provided via anodic oxidation as a metal ion can be identical ordifferent from one another. The present invention therefore comprises,for example, an embodiment according to which the reaction mediumcomprises one or more different salts of a metal and the metal ionpresent in this salt or these salts is additionally provided via anodicoxidation of at least one anode containing said metal. Likewise, thepresent invention comprises an embodiment according to which thereaction medium comprises one or more different salts of at least onemetal and at least one metal different from these metals is provided viaanodic oxidation as a metal ion in the reaction medium.

According to a preferred embodiment of the present invention and inrelation to the electrochemical preparation of MOFs, the at least onemetal ion is provided via anodic oxidation of at least one anodecontaining said at least one metal, no further metal being provided viaa metal salt.

The term “metal” as used within the scope of the present invention inrelation to the electrochemical preparation of MOFs comprises all thoseelements of the Periodic Table of the Elements which can be provided ina reaction medium via anodic oxidation via an electrochemical route andare able to form at least one metal-organic, porous framework materialwith at least one at least bidentate organic compound.

As mentioned above, irrespective of being derived by conventional orelectrochemical methods the use of MOFs as shaped bodies is preferredaccording to the present invention.

Appropriate processes of molding a powder are known to the personskilled in the art, referring, in the broadest sense, to a process,wherein i.e. any powder, powdery substance, array of crystallites etc.,can be formed into a shaped body that is stable under the conditions ofits intended use.

In addition to the optional molding step of a MOF containing powder intoa shaped body the following steps may also occur according to thepresent invention:

-   -   (I) the molding may be preceded by a step of mixing,    -   (II) the molding may be preceded by a step of preparing a        paste-like mass or a fluid containing the MOF containing powder,        for example by adding solvents, binders or other additional        substances,    -   (III) the molding may be followed by a step of finishing, in        particular a step of drying.

The conversion step of molding, shaping or forming and the like may beachieved by any method known to an expert to achieve agglomeration of apowder, a suspension or a paste-like mass. Such methods are described,for example, in Ullmann's Enzylopädie der Technischen Chemie, 4^(th)Edition, Vol. 2, p. 313 et seq., 1972, whose respective content isincorporated into the present application by reference.

In general, the following main pathways can be discerned: (i)briquetting, i.e. mechanical pressing of the powdery material, with orwithout binders and/or other additives, (ii) granulating (pelletizing),i.e. compacting of moistened powdery materials by subjecting it torotating movements, and (iii) sintering, i.e. subjecting the material tobe compacted to a thermal treatment. The latter is somewhat limited forthe material according to the invention due to the limited temperaturestability of the organic materials (see below).

Specifically, the molding step according to the invention is preferablyperformed by using at least one method selected from the followinggroup: briquetting by piston presses, briquetting by roller pressing,binderless briquetting, briquetting with binders, pelletizing,compounding, melting, extruding, co-extruding, spinning, deposition,foaming, spray drying, coating, granulating, in particular spraygranulating or granulating according to any process known within theprocessing of plastics or any combination of at least two of theaforementioned methods.

The molding may be affected by extrusion in conventional extruders, forexample such that result in extrudates having a diameter of, usually,from about 1 to about 10 mm, in particular from about 1.5 to about 5 mm.Such extrusion apparatuses are described, for example, in Ullmann'sEnzylopädie der Technischen Chemie, 4th Edition, Vol. 2, p. 295 et seq.,1972. In addition to the use of an extruder, an extrusion press ispreferably also used for molding.

The preferred process of molding is performed at elevated pressure, i.e.by pressing of the MOF containing powder. The pressure may range fromatmospheric pressure to several 100 bar. Also elevated temperatures(ranging from room temperature to 300° C.) or in a protective atmosphere(noble gases, nitrogen or mixtures thereof) are suitable. Anycombination of these conditions is possible as well.

The conditions under which the pressing may be accomplished depend on,e.g. the press, the filling height, the press capacity, and the form ofthe shaped body.

The step of molding can be performed in the presence of binders and/orother additional substances that stabilize the materials to beagglomerated. As to the at least one optional binder, any material knownto an expert to promote adhesion between the particles to be moldedtogether can be employed. A binder, an organic viscosity-enhancingcompound and/or a liquid for converting the material into a paste can beadded to the metal-organic framework material, with the mixture beingsubsequently compacted in a mixing or kneading apparatus or an extruder.The resulting plastic material can then be molded, in particular usingan extrusion press or an extruder, and the resulting moldings can thenbe subjected to the optional step (III) of finishing, for exampledrying.

A number of inorganic compounds can be used as binders. Non-limitingexamples include titanium dioxide, hydrated titanium dioxide, hydratedalumina or other aluminum-containing binders, mixtures of silicon andaluminum compounds, silicon compounds, clay minerals, alkoxysilanes, andamphiphilic substances.

Other conceivable binders are in principle all compounds used to datefor the purpose of achieving adhesion in powdery materials. Compounds,in particular oxides, of silicon, of aluminum, of boron, of phosphorus,of zirconium and/or of titanium are preferably used. Of particularinterest as a binder is silica, where the SiO₂ may be introduced intothe shaping step as a silica sol or in the form of tetraalkoxysilanes.Oxides of magnesium and of beryllium and clays, for examplemontmorillonites, kaolins, bentonites, halloysites, dickites, nacritesand anauxites, may furthermore be used as binders. Tetraalkoxysilanesare particularly used as binders in the present invention. Specificexamples are tetramethoxysilane, tetraethoxysilane, tetrapropoxysilaneand tetrabutoxysilane, the analogous tetraalkoxytitanium andtetraalkoxyzirconium compounds and trimethoxy-, triethoxy-, tripropoxy-and tributoxy-aluminum, tetramethoxysilane and tetraethoxysilane beingparticularly preferred.

The binder may have a concentration of from 0.1 to 20% by weight.Alternatively, no binder is used.

One or more mold release agent may be present as additives. Suitableagents are graphite or MOF materials, where the MOF has a layercomposition.

In addition, organic viscosity-enhancing substances and/or hydrophilicpolymers, e.g. cellulose or polyacrylates may be used. The organicviscosity-enhancing substance used may likewise be any substancesuitable for this purpose. Those preferred are organic, in particularhydrophilic polymers, e.g., cellulose, starch, polyacrylates,polymethacrylates, polyvinyl alcohol, polyvinylpyrrolidone,polyisobutene and polytetrahydrofuran. These substances primarilypromote the formation of a plastic material during the kneading, moldingand drying step by bridging the primary particles and moreover ensuringthe mechanical stability of the molding during the molding and theoptional drying process.

There are no restrictions at all with regard to the optional liquidwhich may be used to create a paste-like substance, either for theoptional step (I) of mixing or for the step of molding. In addition towater, alcohols may be used, provided that they are water-miscible.Accordingly, both monoalcohols of 1 to 4 carbon atoms and water-misciblepolyhydric alcohols may be used. In particular, methanol, ethanol,propanol, n-butanol, isobutanol, tert-butanol and mixtures of two ormore thereof are used.

Amines or amine-like compounds, for example tetraalkylammonium compoundsor aminoalcohols, and carbonate-containing substances, such as calciumcarbonate, may be used as further additives. Such further additives aredescribed in EP-A 0 389 041, EP-A 0 200 260 and WO 95/19222, which areincorporated fully by reference in the context of the presentapplication.

Most, if not all, of the additive substances mentioned above may beremoved from the shaped bodies by drying or heating, optionally in aprotective atmosphere or under vacuum. In order to keep themetal-organic framework intact, the shaped bodies are preferably notexposed to temperatures exceeding 300° C. However, studies show thatheating/drying under the aforementioned mild conditions, in particulardrying in vacuo, preferably well below 300° C. is sufficient to at leastremove organic compounds out of the pores of the metal-organicframework. Generally, the conditions are adapted and chosen dependingupon the additive substances used.

The order of addition of the components (optional solvent, binder,additives, metal-organic framework material) is not critical. It ispossible either to add first the binder, then, for example, themetal-organic framework material and, if required, the additive andfinally the mixture containing at least one alcohol and/or water or tointerchange the order with respect to any of the aforementionedcomponents.

As far as the optional step (I) of mixing is concerned, for example, ofthe powder containing a metal-organic framework and a binder andoptionally further process materials (=additional materials), allmethods known to the expert in the fields of materials processing andunit operations can be used. If the mixing occurs in the liquid phase,stirring is preferred, if the mass to be mixed is paste-like, kneadingand/or extruding are preferred and if the components to be mixed are allin a solid, powdery state, mixing is preferred. The use of atomizers,sprayers, diffusers or nebulizers is conceivable as well if the state ofthe components to be used allows the use thereof. For paste-like(originating from MOF containing powder) and powder-like materials theuse of static mixers, planetary mixers, mixers with rotating containers,pan mixers, pug mills, shearing-disk mixers, centrifugal mixers, sandmills, trough kneaders, internal mixers, internal mixers and continuouskneaders are preferred. It is explicitly included that a process ofmixing may be sufficient to achieve the molding, i.e., that the steps ofmixing and molding coincide.

EXAMPLES Example 1

FIG. 2 shows the curves for the uptake of propane in a bottle (volume0.5 1) at room temperature with and without MOF. The MOF used in thisexample is Zn-MOF-5. The preparation of that MOF is described in US2003/0148165 A1.

The ratios of the pressures with/without MOF at certain uptake valuesare shown in table 1. TABLE 1 Uptake propane 6.32 10.16 30.5 (g/lcontainer without MOF) Pressure of container without MOF 3.244 5.0369.808 (= p_(empty)) in bar Necessary pressure of container with MOF0.107 0.161 0.324 for the same uptake (= p_(MOF)) in bar$\frac{p_{MOF}}{p_{empty}}$ 0.03 0.03 0.03

Example 2

FIG. 3 shows the curves for the uptake of propane in a bottle (volume0.477 1) at room temperature with and without MOF. The MOF used in thisexample is IRMOF-8. The preparation of that MOP is described in WO-A02/088148.

The ratios of the pressures with/without MOF at certain uptake valuesare shown in table 2. TABLE 2 Uptake propane 3.5 9.77 16.29 20.57 (g/lcontainer without MOF) Pressure of container without MOF 2.023 5.1218.012 9.681 (= p_(empty)) in bar Necessary pressure of container with0.090 0.203 0.315 0.408 MOF for the same uptake (= p_(MOF)) in bar$\frac{p_{MOF}}{p_{empty}}$ 0.04 0.04 0.04 0.04

1. A method of storing a liquefied gas in a container having an entranceopening and optionally a separate exit opening for allowing theliquefied gas to enter or exit the container and a gas-tight maintainingmechanism capable of maintaining the liquefied gas in its gaseous statein a predefined amount and under a predefined pressure inside thecontainer and containing a metal-organic framework material (MOF)comprising at least one metal ion and at least one at least bidentateorganic compound, which is coordinately bound to said metal ion, whereinthe ratio of the pressure in the container to a pressure necessary forthe storage of the same amount of liquefied gas at the same temperaturein the container without comprising the MOF is at most 0.2.
 2. Themethod of claim 1, wherein the liquefied gas is selected from the groupconsisting of halogenated C₁-C₁₀ hydrocarbon, propane, butane, isobutaneand mixtures thereof.
 3. The method of claim 2, wherein the liquefiedgas is propane.
 4. The method of claim 1, wherein the container is of anon-cylindrical shape.
 5. The method of claim 1, wherein the pressure ismore than 0.1 bar and less than 20 bar.
 6. The method of claim 1,wherein the amount of liquefied gas is at least 2 g/l.
 7. The method ofclaim 1, wherein the ratio is at most 0.1.
 8. A container filled withliquefied gas in a predefined amount and under a predefined pressurehaving an entrance opening and optionally a separate exit opening forallowing the liquefied gas to enter or exit the container and agas-tight maintaining mechanism capable of maintaining the liquefied gasin its gaseous state in a predefined amount and under a predefinedpressure inside the container and containing a metal-organic frameworkmaterial (MOF) comprising at least one metal ion and at least one atleast bidentate organic compound, which is coordinately bound to saidmetal ion, wherein the ratio of the pressure in the container to apressure necessary for the storage of the same amount of liquefied gasat the same temperature in the container without comprising the MOF isat most 0.2.
 9. A process for filling a container having an entranceopening and optionally a separate exit opening for allowing theliquefied gas to enter or exit the container and a gas-tight maintainingmechanism capable of maintaining the liquefied gas in its gaseous stateinside the container and containing a metal-organic framework material(MOF) comprising at least one metal ion and at least one at leastbidentate organic compound, which is coordinately bound to said metalion, with a liquefied gas up to a predefined amount and a predefinedpressure so that the ratio of the pressure in the container to apressure necessary for the storage of the same amount of liquefied gasat the same temperature in the container without comprising the MOF isat most 0.2, comprising the step contacting the entrance opening of thecontainer with a bottle of the liquefied gas, wherein the gas is in itsliquid state or compressed state, such that the pressure in the feedcontainer exceeds the pressure in the container which is to be filled.10. Use of a container according to claim 8 for the controlled releaseof liquefied gas.